Support adjuvant for improved vanadium polymerization catalyst

Abstract

A vanadium catalyst component for the polymerization of 1-olefins and a process for making said catalyst component are disclosed. The catalyst component is prepared by fluoriding a support comprising silica. Use of the catalyst component provides a catalyst with increased activity, increased response to hydrogen for chain termination, increased response to comonomer for resin density reduction, and allows the molecular weight distribution of the polymers to be independently controlled by controlling the amount of fluorination and the fluorination temperature.

What is claimed is: 
     
       1. A fluorided supported vanadium catalyst component for polymerizing olefins to polyolefins of controlled molecular weight distribution as a function of the fluorine to vanadium metal ratio of said catalyst component and of the fluorination temperature, comprising a product of reacting: (a) a fluorided support material comprising silica; and   (b) a vanadium compound of the general formulas: ##STR4## where "x" is a number from 0 to 3 and R is a hydrocarbon radical, VCl y  (OR) 4-y     where "y" is a number from 3 to 4 and R is a hydrocarbon radical, ##STR5## where "z" is a number from 2 to 3 and (AcAc) is an acetyl acetonate group, ##STR6## where (AcAc) is an acetyl acetonate group, or VCl 3 .nL where "n" is a number from 2 to 3 and L is a Lewis base which can form hydrocarbon-soluble complexed with VCl 3  ; wherein fluorine and vanadium are present in said product of reaction in a mole ratio of fluorine to vanadium of from 0.005 to about 20, and wherein there is no substantial reaction of the fluorided support material with another catalyst component prior to contact between the vanadium compound and the fluorided support material.     
     
     
       2. The supported catalyst component of claim 1 further comprising a halogenating agent. 
     
     
       3. The supported catalyst component of claim 1 wherein said support material is fluorided by dry mixing a fluorine containing compound with said support material and heating the mixture to a temperature of between 200° C. and 1,000° C. 
     
     
       4. The supported catalyst component of claim 1 further comprising a product of reacting a slurry of said support material and an organoaluminum compound of the formula R' m  AlX 3-m  wherein R' represents an alkyl group, cycloalkyl group or aryl group, X represents a halogen atom and "m" represents a number equal to or greater than 1 and less than or equal to 3. 
     
     
       5. The supported catalyst component of claim 1, wherein support material consists of fine, dehydrated support material, selected from the group consisting of silica, and silica-alumina mixtures. 
     
     
       6. The supported catalyst component of claim 1 wherein said support material is fluorided using a fluorine containing compound such as hydrogen fluoride, fluorides of ammonium and metals, and complex fluorides of ammonium and metals. 
     
     
       7. The supported catalyst component of claim 1, wherein the support material is silica. 
     
     
       8. The supported catalyst component of claim 1, wherein vanadium metal is present in the product of reaction in a concentration of from about 0.05 to about 2.0 millimoles of vanadium per gram of dried support. 
     
     
       9. The supported catalyst component of claim 1, wherein aluminum metal is present in the product of reaction in a concentration of from about 0.05 to about 5.0 millimoles of aluminum metal per gram of dried support. 
     
     
       10. The supported catalyst component of claim 1, wherein fluorine and vanadium are present in said product of reaction in a mole ratio of fluorine to vanadium of from 0.005 to about b 10.0. 
     
     
       11. A process for preparing a supported catalyst material, comprising the steps of: (a) fluoriding a support material comprising silica; and   (b) treating said fluorided support material with (i) a vanadium compound of the general formulas: ##STR7## where "x" is a number from 0 to 3 and R is a hydrocarbon radical, VCl y  (OR) 4-y     where "y" is a number from 3 to 4 and R is a hydrocarbon radical, ##STR8## where "z" is a number from2 to 3 and (AcAc) is an acetyl acetonate group, ##STR9## where (AcAc) is an acetyl acetonate group, or VCl 3 .nL where "n" is a number from 2 to 3 and L is a Lewis base which can form hydrocarbon-soluble complexes with VCl 3  ; and wherein there is no substantial reaction of the fluorided support material with another catalyst component prior to contact between the vanadium compound and the fluorided support material.     
     
     
       12. The process of claim 11 wherein the fluorided support material is combined with a hydrocarbon to form a hydrocarbon slurry, the hydrocarbon slurry is treated with the vanadium compound and thereafter treating said hydrocarbon slurry with a halogenating agent. 
     
     
       13. The process of claim 11 wherein said fluoriding of said support material is achieved by dry mixing a fluorine containing compound with said support material and heating the mixture to a temperature to between 200° C. and 1,000° C. 
     
     
       14. The process of claim 11 comprising forming a hydrocarbon slurry of fluorided support, treating the hydrocarbon slurry with the vanadium compound and thereafter reacting said hydrocarbon slurry with an organoaluminum compound of the formula R' m  AlX 3-m  wherein R' represents an alkyl group, cycloalkyl group or aryl group, X represents a halogen atom and "m" represents a number equal to or greater than 1 or less than or equal to 3. 
     
     
       15. The process of claim 11 wherein the said support material consists of fine, dehydrated support material, selected from the group consisting of silica and silica-aluminum mixtures. 
     
     
       16. The process of claim 11 wherein said fluoriding of said support material is achieved by using a fluorine containing compounds such as hydrogen fluoride, fluorides of ammonium and metals, and complex fluoride, of ammonium and metals. 
     
     
       17. The process of claim 11 wherein said support material consists of silica. 
     
     
       18. The process of claim 11 wherein said vanadium metal compound is added to yield a concentration from about 0.05 to about 2.0 millimoles of vanadium per gram of dried support. 
     
     
       19. The process of claim 11 wherein said aluminum metal is added to yield a concentration from about 0.05 to about 5.0 millimoles of aluminum metal per gram of dried support. 
     
     
       20. The process of claim 11 wherein said fluorine and vanadium are added to yield a mole ratio of fluorine to vanadium of from 0.005 to about 10.0.